TRIPHENYL  METHANE  COMPOUNDS 


X ^ 


,^i'*'  ■ 'T"'^ 


UNIVERSITY  OF  ILLINOIS 


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QMN__MApFQRB_0^^^  

ENTITLED 


IS  APPROVED  BY  ME  AS  FULFILLING  THIS  PART  OF  THE  REQUIREMENTS  FOR  THE 
DEGREE  OF a_e_l P_r _ _qf _ _S  c_i p n ^ e _ _iij_ _C he_nLis  t_rj_ 


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Digitized  by  the  Internet  Archive 

in  2016 


https://archive.org/details/triphenylmethaneOOgran 


lEDEX 


I. 

II. 

III. 

IV. 

Y. 

VI. 


Introduction 

Historical 

Theoretical  Consideration 

Experimental 

SUiTunary 

Bibliography 


1 

2 

3 

17 

26 

27 


OBG/SW 


ACZUOWLEDGiiMSHT 

I wish  to  express  my  sincere  gratitude 
and  appreciation  to  Dr.  .Eoger  Adams  for  the 
assistance  and  inspiration  given  me  during 
the  course  of  these  experiments. 


fl) 

I. 

INTEODUCTIOH 

In  spite  of  the  fact  that  dyes  of  the  triphenyl  methane 
series  are  among  those  first  hnov/n  and  at  present  have  a very 
extended  use,  methods  for  their  production  are  unsatisfactory, 
giving  low  yields  and  often  their  structure  is  misunderstood 
or  even  unhnown.  Hence,  any  work  which  will  improve  yields 
and  throw  light  on  the  structure  of  these  compounds  v/ill  he 
welcomed  hy  both  the  theoretical  chemist  and  the  dye  plant 
enterpreneur . 

The  following  i/vork  was  undertaken  with  this  object  in 
view,  with  special  emphasis  on  improvements  in  methods  of  pro- 
ducing Spirit  Blue  dyes.  Direct  synthesis  was  attempted,  thus 
eliminating  the  possibility  of  the  many  side  reactions  so  detri- 
mental in  the  common  process  which  is  the  phenylation  of  fuchsine. 


a; 


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m:.it 


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,■«  *.  m 
■::<W 


(2) 


II. 

HISTORICAL 

The  first  known  artificial  dyes  vt^ere  those  of  the 
triphenyl  methane  type  and  v/ere  discovered  at  approximate- 
ly the  same  time,  1856-58  hy  chemists  of  England,  France, 
and  Germany.  Hathanson  is  given  priority,  w^hile  f erkins , 
Hoffman,  Eoguencount  and  Tort  follow  in  line. 

Since  then  great  Strides  have  taken  place  in  their 
manufacture,  hut  due  to  the  fact  that  owners  keep  their 
processes  as  secret  as  possible  very  little  information  has 
been  published. 

Girard  and  de  Laire  are  accredited  with  the  discovery 
of  triphenyl  rosaniline  in  1862. 

The  method  upon  v/hich  the  following  work  is  based  was 
discovered  in  189E  by  chemists  of  Geigy  & Company,  Basel, 
Switzerland.  A patent  of  that  year  describes  the  process. 
Since  then,  no  work  has  been  published  on  it. 


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III. 


TT) 

TEEOEEIICAL  COESIEERA-TIOES 

Spirit  Blue  is  described  in  the  literature  as  tripheny- 
lated  rosaniline, 

XZ3'*^<IZ> 

\ — >«-<  > 

and  Alkali  Blue,  Soluble  Blue,  and  V/ater  Blue  as  the 
mono,  di,  and  trisulphonic  acids  respecively.  'The  sulphonic 

group  goes  para  to  the  amino  group.  Liore  or  less  is  to  be 

V 

found  on  methods  of  their  preparation,  but  this  is  practically 
all  that  may  be  found  on  the  struct  of  these  compounds. 

The  common  method  of  making  Spirit  Blue  and  its  de- 
rivatives is  to  first  prepare  Buchsine  by  heating  a mixture 
of  aniline,  aniline  hydrochloride,  para  toluidine,  nitrobenzene, 
zinc  chloride,  and  iron  oxide  at  160  degrees  for  twelve  hours, 
llie  resulting  low  yields  are  readily  understood  when  the  complex- 
ity of  this  mixture  is  considered.  Birst  toluene  is  oxidized  by 
the  nitrobenzene  to  p-amino  benzaldehyde.  This  in  turn  condenses 
with  two  mols  of  aniline  to  give  the  leuco  base. 


Upon  further  oxidation  by  the  nitrobenzene  this  yields 


vvhich  inimediately  forms  luchsine  with  the  hydrochloric  acid 
present  in  the  aniline  hydrochloride. 

It  is  highly  improbable  that  all  these  reactions  could 
take  place  simaltaneously  in  one  mixture  and  give  the  best  re- 
sults. The  importance  of  correct  temperatures  for  various  re- 
actions is  only  too  well  known.  Furthermore  the  presence  or 
absence  of  acid,  water,  or  catalyzer  may  promote  one  reaction 
and  retard  another,  h'ith  all  these  in  one  mixture  we  have  no 
method  of  control,  which  w/ould  make  them  function  properly  for 
each  reaction. 

Perhaps  even  more  important  than  incomplete  reactions 
are  the  formation  of  many  undesirable  products,  so  called  side 
reaction  products.  In  fact  these  make  up  the  greater  part  of 
the  product  and  represent  at  least  70^  loss  on  the  wei^.t  of  the 
materials  used. 

The  possible  side  reactions  are  too  many  to  enumerate. 
It  is  sufficient  to  say  that  the  finished  Fuchsine  melt  contains 
only  12  to  15^  pure  color. 

A typical  analysis  is: 


Pure  color 

13% 

Aniline  oil 

7^ 

Kesidue 

65% 

Moisture 

26^ 

(5) 


The  formation  of  Rosaniline  is  easily  accomplished  hy  add- 
ing sodium  hydroxide  solution  to  a solution  of  Ruchsine.  The 
reaction  proceeds  almost  quantitatively. 

Information  on  the  chemistry  of  phenylation  is  entirely 
lacking,  ^he  literature  merely  states  that  v/hen  a mixture  of 
Rosaniline  and  aniline  are  heated  together  v/ith  the  proper 
catalyst,  triphenyl  rosaniline  is  fonned.  If  this  were  the 
case,  only  one  shade  of  blue  could  he  obtained  v/hile  in 
practice,  shades  ranging  from  a very  reddish  blue  to  a green- 
ish blue  are  readily  obtained  by  proper  control  of  the  re- 
action. 

The  various  shades  are  merely  different  degrees  of 
phenylation.  Thus 


is  a very  red  shade  blue. 


H 


>A/-<Z3 


H 


a pure  blue  and 


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(6) 

a very  green  shade  blue.  Actually,  the  product  is  a mixture 
of  the  above  and  may  be  separated  by  their  difference  of 
solubilities  in  aniline  hydrochloride.  Even  samples  of 
the  greenest  shade  blues  are  found  to  contain  a very  small 
amount  of  the  monophenylated  product. 

Yields  are  fairly  satisfactory,  being  70  to  80^  of 
theoretical.  It  is  cut  down  by  aniline  reacting  v/ith 
itself  to  form  diphenylomine  and  also  hosaniline  mole- 
cules condensing  with  themselves. 


The  greatest  disadvantage  in  this  process  is  that  the 
shade  cannot  be  controlled.  It  is  impossible  to  run  dipli 
cate  melts  v/hich  give  identical  shades.  Furthermore,  the 
greenest  possible  shade  is  not  obtainable  by  this  method, 
for  the  reason  that  the  Eosaniline  molecules  will  not  re- 
act completely  v/ith  aniline  to  form  the  triphenylated 
product.  Some  mono  and  diphenylated  rosaniline  is  always 
present  in  the  finished  melt.  Then  too,  the  longer  the 
reaction  is  carried  out,  the  lower  will  be  the  and 

as  the  dye  users  demand  a green  shade,  considerable  loss 

occurs  in  prolonging  the  phenylation  in  order  to  obtain 
these  green  shades. 


(7) 


In  view  of  these  facts  a synthesis  which  i/vould  give  pure 
compounds  would  insure  uniform  shades  and  improve  yields. 

The  sulphonation  of  Spirit  Blue  goes  easily,  inasmuch 
as  95^  sulphuric  acid  is  sufficiently  strong  to  give  any 
degree  of  sulphonation,  vis.  from  a mono  to  a trisulphonated 
product.  However,  greatest  care  in  temperature  control  and 
length  of  time  must  he  exercised.  Strict  trade  specifications 
require  that  the  solubility  in  sulphuric  acid  solution  be 
exact  for  the  respective  dyes  Alkali,  Soluble  and  Water  Blues. 
Careful  chemical  control  is  necessary  and  even  then  many 
batches  are  oversulphonated. 

Different  shades  require  different  lengths  of  time  for 
sulphonation,  also  different  proportions  of  acid  to  Spirit 
Blue.  Prolonged  sulphonation  or  too  strong  acid  weakens 
the  resulting  dye. 

Thus  it  is  seen  that  the  many  factors  entering  into 
sulphonation  make  the  present  method  unsatisfactory. 

In  view  of  the  fact  that  yields  on  Puchsine  are  very 
low  and  accurate  control  of  phenylation  and  sulphonation 
are  impossible,  the  present  method  of  production  of  Spirit 
Blue  and  its  derivatives  is  very  unsatisfactory. 


The  possibilities  of  the  new  process  have  never  been 


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The  reactions  taJce  place  in  two  steps.  Heaction  one 
is  the  first  step  and  the  remainder  of  the  reactions  the 
second  step. 

The  resulting  product  has  a much  greener  shade  than 
any  product  obtained  from  the  old  process  and,  as  would 
he  expected,  is  very  soluble. 

The  conditions  for  this  reaction  are  ideal.  The 
possibilities  of  side  reactions  are  very  small.  The  sul- 
phonic  group  makes  the  para  hydrogen  of  the  diphenylamine 
very  reactive  enabling  the  condensation  to  proceed  very 
easily,  ho  condensation  agent  is  required.  In  fact,  the 
presence  of  more  than  a very  small  amount  of  hydrochloric 
or  sulphuric  acids  yields  a hard  insoluble  product. 

Again  in  the  second  step,  the  possibility  of  side 
reactions  is  neglegible.  Thus  in  the  reaction 


the  third  molecule  of  diphenylamine  monosulphonic  acid  must 
go  in  the  right  place  or  not  at  all. 

The  most  desired  dye  of  the  Spirit  Blue  series  is  Allcali 
Blue  which  contains  only  one  sulphonic  acid  group.  The  red 


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shade  could  be  obtained  by  oxidizing  a diphenylamine  mono- 
sulphonic  acid  group  on 


and  the  green  shade  from 

^ cy^^~<z>so,H 


The  intermediate  blue  shade  could  be  made  by  mixing 
the  red  and  green  shades  in  the  proper  proportion. 

In  order  to  produce  the  green  shade  by  the  above  method, 
the  present  low  yield  obtained  in  the  preparation  of 


H 

H 


\ 


c 


would  have  to  be  raised 


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For  Soluble  Blue  dyes 


fll) 


o< 


v.’ould  give  a blue  shade  and 

^ /<!> 


^ 0^-0 


a green  shade. 

The  procedure  for  mahing  Water  Blue,  the  trisulphonated 
compound,  has  already  been  given  above,  i.Iany  other  shades 
could  be  obtained  by  using  dimethylaniline  in  various  com- 
binations. 

Certain  facts  brought  out  in  experiments  with  these 
dyes  have  demonstrated  that  much  is  to  be  learned  about 
their  structure.  The  colloidal  nature  of  these  compounds 
is  shown  in  certain  tests  which  the  manufacturers  make. 

The  specifications  of  Alkali  Blue  for  lithographic  inks 
require  that  v/hen  two  grams  of  the  sample  is  dissolved 
in  100  cc.  of  water,  it  shall  be  precipitated  with  1.3  cc. 
of  ten  times  diluted  93%  sulphuric  acid.  As  the  acid  is 


T.^rr^TT— ■; 

added.,  an  extremely  fine  precipitate  first  appears,  then  as 
the  end  point  is  reached  a heavy  precipitate  suddenly  appears. 
If  the  solution  is  made  up  to  200  cc.  instead  of  100  cc. , just 
twice  as  much  acid  is  required  to  cause  precipitation,  showing 
that  the  concentration  of  the  acid  only  is  the  determining 
factor.  Soluble  Blue  (the  disulphonic  acid  compound)  requires 
about  17  cc.  of  the  standard  acid  to  cause  precipitation. 

Water  Blue  cannot  be  precipitated  with  any  amount  of  acid. 

A study  of  the  colloidal  nature  of  the  various  sulphonated 
blues  should  prove  a valuable  contribution  to  this  branch 
of  chemistry. 

Varying  conditions  in  the  last  steps  of  Akali  Blue  manu- 
facture produce  dyes  which  require  more  or  less  of  the 
standard  acid  for  their  precipitation. 

Sodium  hydroxide  is  added  to  the  free  acid  of  Alhali 
Blue  to  form  a soluble  salt.  If  just  sufficient  alhali  is 
added  to  render  it  soluble,  2.5  to  S.O  cc.  of  the  standard 
acid  is  required  for  precipitation.  If  now  more  alkali  is 
added  so  that  the  finished  dye  v/ill  contain  approximately 
tw'ice  as  much  sodium,  it  v/ill  be  precipitated  with  less 
than  half  the  amount  of  acid  than  that  required  for  the  same 
dye  containing  less  alkali. 

The  rate  and  temperature  at  'which  the  Alkali  Blue  solution 
is  evaporated  also  cause  a marked  change  in  the  precipitation 
point.  It  would  seem  from  the  above  that  Alkali  Blue  possesses 


(12) 


two  structures*  The  one  usually  given  is 


I'rom  certain  experimental  facts  and  also  the  well  estab- 
lished structure  of  the  simpler  triphenylme thane  dyes  it 
seems  reasonable  to  believe  that  Alkali  Blue  possesses 
the  following  structure: 


The  structure  for  Spirit  Blue  from  which  Alkali  Blue  is 
derived  is  well  established* 


The  chlorine  is  firmly  attached  for  it  can  not  be  split 
off  even  with  boiling  sodium  hydroxide* 

When  concentrated  sulphuric  acid  is  added  to  this  com- 
pound, hydrochloric  acid  is  iiomediately  given  off*  It  seems 
logical  to  believe  that  the  hydrochloric  acid  is  merely  dis- 
placed and  that  the  sulphuric  acid  goes  on  in  it  place  to  give 


c 


'■  )V 

t ' ' 


•• 

4 At 


:1 


i f I . 


. r 


/ 


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* j I Jt  Xv 


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♦ 


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'.  ^ >*  r'Ault^.  .lliri  I <V.. 


fl4) 


^ o V - -o 
^ — O*  — o 


Upon  continued  action  of  the  sulphuric  acid,  sul- 
phonation  takes  place.  The  melt  is  then  poured  into 
water  and  vi/ashed  acid  free,  and  sodium  hydroxide  added 
until  material  is  completely  dissolved.  If  just  enough 
sodium  hydroxide  is  added,  the  product  is  completely 
soluble  and  is  a deep  blue  color.  It  must  possess  the 
quinoid  structure  because  it  is  colored.  This  is  easily 
explained  if  we  assume  the  hydrogen  of  the  free  sulphonic 
acid  is  replaced  by  the  sodium  to  give 


If  now  more  sodium  hydroxide  is  added,  the  solution 
becomes  weaker  and  v;hen  approximately  twice  as  much  sodium 
hydroxide  is  added,  the  solution  becomes  colorless.  The 
second  addition  of  alkali  removes  the  sulphuric  acid  from 
the  nitrogen  to  give  the  base  thusly. 


c 


0^-0 

^ H-  _ 


\ 


■O  N 


fl5) 


just  sodium  hydroxide  removes  the  hydrochloric  acid  from 
Fuchs ine  and  gives  the  hase. 


HO  - C 


O it/, 

O Y 

If  now  sulphuric  acid  is  added,  a deep  "blue  precipitate 
is  formed.  This  is  the  same  compound  that  was  originally 
formed  in  the  melt* 


There  is  no  reason  to  "believe  that  these  phenylated 
rosanilines  should  react  different  than  the  corresponding 
alkylated  compounds.  Thus 


N 

■On 

0*-/v 


\ 


' cfYj 

■ C.f/j 

- H 

■ H 
Cl 


(16) 


reacts  Vvith  sodium  hydroxide  to  give 


HO^C 


<3 


a colorless  compound  and  when  this  "base  is  treated  with 
hydrochloric  or  sulphuric  acid  the  original  color  is  re- 
stored. 

The  behavior  of  Alkali  Bluei,  as  well  as  the  general 
reactions  for  this  type  of  compounds  indicate  that 


V ^ 


<3 

-<3  A'  ^ <3 


is  its  true  formula.  To  prove  conclusively,  an  analysis 
would  have  to  made  on  the  free  acid  of  Alkali  Blue. 


^ A'-aA^«^aabl.V 


V'  '■'(’  ' ' , >1''  I . ' '.  •■  - • ’' 


: .:n; 


: 'M^3 


, ' ^ i^  JL  0 /S  * Kj  T ‘j-i-i  sliffjh  • .“S-t  -,v  J5f  rt-  V 


Nil 


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IV, 


fl7) 

Condensation  of  I-iphenylamine. 

Experiment  I. 

50  g.  of  diphenylamine  was  dissolved  in  100  cc«  of 
ethyl  alcohol  in  a round  bottom  flask  and  11.1  g.  of  40^ 
formaldehyde  added.  The  temperature  was  raised  to  60  de- 
grees and  2.5  cc.  of  20^  hydrochloric  acid  added.  Vigor- 
our  reaction  took  place  immediately.  Flame  v;as  removed 
but  temperature  rose  to  82  degrees,  then  gradually  sank. 

At  the  end  of  15  minutes  no  odor  of  formaldehyde  v/as  pre- 
sent and  Fuchs ine  aldehyde  reagent  gave  negative  test.  A 
heavy  viscous  brown  liquid  soon  settled  on  the  bottom, 
v;hile  the  upper  layer  remained  turbulent.  The  contents 
were  allov;ed  to  stand  two  days,  during  which  time  the  brown 
layer  became  hard.  This  solid  v;as  extracted  with  three  100  cc. 
portions  of  ethyl  alcohol.  27  g.  of  diphenylamine  w^as  re- 
covered by  precipitating  it  from  the  alcohol  w^ith  water. 

The  yield  of  diphenyldiamino  diphenylme thane  was  7.5  a 

=15^. 

M.  P.  79  to  90  degrees.  It  did  not  give  a sharp  melting 
point. 

The  material  was  dissolved  in  50^  sulphuric  acid  and  the 
solution  poured  into  water.  The  resulting  precipitate  was 
dried. 

Weight  7g. 

M.  1.  95  to  100  degrees. 


~ ' '♦•  V.'  * ‘*  «*»W  ••iN— 


0 


' I 


1 * ' *i‘  * i ^ ' ^ 


7'.  ,: 


-.} 


i.  'i  j ■ ■ - V 


'i  .■■'  .'■‘^*4  1 i. '..  - i' 


sL'7 


'■  I'-.i/--,  ■'  ' f’C  ■''■*■ 


'I 


'’  4 - 

« V,  ■ 

#*4,  ^ ^ 5*. 


'J  1 O f 


Experiment  II. 


mf 


This  experiment  was  a duplicate  of  experiment  one  up  to 
the  point  of  extraction.  In  this  experiment  the  hrown  solid 
was  extracted  with  three  100  cc.  portion  of  ether. 

Recovered  Diphenylamine  S3  g. 

Yield  8 g. 

M-  P.  145  to  150. 

The  diphenyldiaminodiphenylmethane  was  recrystalized 
from  benzene. 

M.  P.  155  to  159. 

Oxidation  of  diphenyldiaminodiphenylmethane. 

Experiment  III. 

A saturated  solution  containing  10  g.  of  copper  sulphate 
was  poured  over  40  g.  of  sodium  chloride  and  the  vdiole  dried. 
6 g.  of  diphenyldiamino diphenyl  methane  was  dissolved  in  3 g. 
of  phenol  and  6 g.  of  diphenylamine  and  poured  over  the  above 
salt,  heated  at  65  to  70  degrees  for  24  hours.  A very  good 
blue  color  resulted,  but  no  means  of  purification  could  be 
found. 

Sulphonation  of  Diphenylamine. 

Experiment  IV. 

6 mols  of  acid  to  5 of  diphenylamine. 

85  g.  of  diphenylamine  was  melted  in  an  evaporating  dish 


(19 


dish  and  54  cc.  of  95$^  sulphuric  acid  added.  The  mass  became 
very  viscous  and  hard  to  stir  and  soon  turned  black  after  the 
temperature  had  been  raised  to  160  degrees. 

Considerable  sulphur  dioxide  was  given  off.  After  one 
hour  heating  at  160  degrees  the  mixture  Vs/as  found  to  be  in- 
soluble in  alkali  and  alcohol.  The  diphenylamine  had  been 
oxidized. 


54  g.  of  diphenylamine  was  heated  to  lEO  degrees  in  a 
400  cc.  beaker  and  6 cc.  of  sulphuric  acid  (95fo)  added  with 
stirring. 

The  color  of  the  mass  Vvas  light  green  and  it  soon  became 
very  viscous.  Temperature  was  raised  to  160  degrees  which 
caused  effervescence  to  take  place.  Melt  was  held  at  150  to 
160  degrees  for  40  minutes  and  then  poured  into  EOO  cc.  of 
toiling  W'ater , neutralized  v;ith  lime  and  vhile  solution  ?/as 
hot  it  7v'as  filtered.  The  residue  was  extracted  and  found  to 
contain  14  g.  of  diphenylamine. 

The  filtrate  was  allowed  to  cool  and  the  crystals  of 
calcium  diphenylamine  monosulphonate  filtered  off.  It  was  re- 
crystalized  from  hot  water  and  some  diphenylajuine  separated  on 
the  filterpaper. 


Experiment  V. 

E mols  diphenylamine  1 mol  acid 


Yield  11.5  g of 
Equal  to 


Experiment  VI. 


Experiment  five  was  repeated.  Eeaction  proceeded  the 
same  as  before. 

Yield  9.7  g. 

Equal  to  E9.0/^. 


Experiment  VII. 

1 mol  of  diphenylamine  to  1 of  acid. 

85  g.  of  diphenylamine  v/as  heated  in  an  evaporating 
dish  to  120  degrees  and  28  cc.  of  sulphuric  acid  (95^) 
slowly  added.  At  first  the  liquid  solidified  but  upon 
the  addition  of  the  remainder  of  the  acid  it  again  became 
liquid.  Temperature  was  raised  to  160  degrees  and  held. 
Almost  immediately  sulphur  dioxide  v^as  given  off  and  the 
melt  turned  to  a hard  black  mass.  It  v/as  insoluble  in 
sodium  hydroxide. 


Ibcperiment  VIII. 

1 mol  diphenylamine  to  1 mol  of  50^  sulphuric  acid. 

From  this  experiment  on,  a 400  cc.  flask  provided 
with  an  ajitator  was  used  and  an  oil  bath. 

42  g.  of  diphenylamine  was  melted  in  a flask  and  28  cc. 
of  50^  sulphuric  acid  added.  Temperature  raised  to  160 
degrees;  held  there  for  2 hours  and  then  raised  to  180  de- 
grees. The  v/ater  gradually  evaporated  out  and  the  sulphon- 
ation  then  proceeded  as  in  experiment  seven.  Sulphur  di- 


i ^ 


A •* 


i* 

J . 


..J 


**  •<*•■'  * 


^ - • ’ ^ : L ..  j.  '>  ‘^t  >'<«'H'.  . ^ ht:. 

> •■  V-  •'•  '•  - ' ■ • •'  ■ ■ ^a.  c vi-(r^ 

> , ; , ■ _j  ‘\'  , , '^J*^****  ‘■'5 

i .. .'.  u . V ..  _ < . . J,  >\.  ^ I / ■rt'fi 


x/ 


X 


X 


I 


<■ 


iv  '■ 


< 


■ ,.?.  U j ‘ '■  , .‘  ,.  j ' ■ ; .'  V 


. > 


( »;  V-&' 


;i.L  i’ 


f f 


(21) 


oxide  was  given  off.  The  mass  v/as  boiled  up  with  sodium  hy- 
droxide solution.  A green  powder  resulted  which  had  a M.P. 
over  250  degrees. 

Experiment  IX. 

1 mol  diphenylamine  to  1 mol  of  75^b  sulphuric  acid. 

4S  g.  of  diphenylamine  was  melted  and  14  cc.  of  acid 
plus  4.7  cc.  of  water  added.  The  reaction  and  results  were 
the  same  as  in  experiment  eight. 


Experiment  X. 

2 mols  diphenylamine  to  1 of  acid. 

85  g.  of  diphenylamine  ¥/as  melted  in  the  flask  and  28  cc. 
of  sulphuric  acid  slowly  added.  Considerable  frothing  took 
place.  Temperature  was  raised  to  160  to  170  degrees  and  held 
there  for  six  hours.  Melt  was  poured  into  hot  v/ater  and 
neutralized  with  lime.  Solution  allo?;ed  to  partially  cool  to 
45  degrees  and  filtered.  Upon  cooling  the  calcium  diphenylamine 
monosulphonate  crystalized  out. 

Yield  52  g.  equal  to  46.7^  theoretical. 

Experiment  Jx.X  * 

Experiment  ten  v/as  repeated  holding  the  temperature  be- 
tween 180  and  190  degrees.  After  about  four  hours  heating  the 
temperature  accidentally  ro3e  to  235  to  240  degrees.  Sulphur 
dioxide  was  evolved  and  the  melt  turned  hard  and  black  the 
same  as  when  too  large  a proportion  of  acid  v/as  used. 


(22) 


Experiment  ill. 

Experiment  ten  v/as  repeated  and  the  temperature  held 
at  180  to  190  degrees  for  16  hours.  At  the  end  the  melt 
had  a very  light  pink  color.  It  was  poured  into  hot  v/ater 
limed  and  the  diphenylamine  and  excess  lime  filtered  off  hy 
partial  cooling. 

Yield  of  diphenylamine  monsulphonate  57  g.  equal  to  56.2^ 

Recovered  diphenylamine  54.2  g.  equal  to  42^. 

Experiment  XIII. 

Experiment  twelve  was  repeated  but  this  time  the  sulph- 
onation  melt  was  poured  into  hot  water  and  sodium  carbonate 
added  till  neutral.  Solution  was  cooled  and  the  unreacted 
diphenylamine  filtered  off,  58  g.  equal  to  44.7  recovered. 

The  sodium  siphenylamine  monosulphonate  was  evaporated 
dom  to  dryness  and  used  in  a condensation  experiment. 

Yield  45  g.  

Condensation  of  Calcium  diphfmylamine  monosulphonate. 

Experiment  XI7. 

20  g.  of  the  calcium  salt  was  dissolved  in  100  cc.  of 
water  and  5 cc.  of  40^  formaldehyde  added.  Solution  v/as 
heated  on  water  bath  till  dryness  (4  hours). 

Residue  was  a grey  soluble  solid. 

Yield  19  g.  equal  to  95^. 


-M. ' R d : 


’■rwr" 


^ • "n:  -*  — 


-'.iJ.  . i'- j: 


! ,J  ■/ 


j ' ' J. 


I 

Tii 


’.D 

* i 


. :i  o: 


» j:i  0.-:,  -• 


jiir'iS'.- 


I^periment  XV. 


mj 

This  experiment  was  run  the  same  as  XIV.  except  that 
1 cc.  of  20fo  hydrochloric  acid  was  added  the  solution  to 
catalyze  the  reaction.  As  evaporation  took  place  the  solu- 
tion hecame  brown  and  viscous.  At  the  end  the  residue  was 
hard  and  dark  brovm  and  insoluble  in  water. 

Various  methods  of  oxidation  were  attempted  but  no  color 
could  be  obtained.  The  hydrochloric  acid  proved  very  detri- 
mental to  the  condensation. 

Experiment  XVI. 

This  Vifas  run  the  same  as  experiment  XIV.  except  that  a 
few  drops  of  sodium  hydroxide  was  added  to  mal:e  it  distinctly 
alkaline.  The  residue  was  a very  light  grey  and  water  soluble. 
That  it  was  only  a partial  condensation  was  shown  vh  en  it  was 
oxidized  to  the  color. 

Yield  19.5  g.  equal  to  95.6/'o 

Oxidation  to  the  Dye. 

Experiment  XVII. 

10  g.  of  the  condensation  product  v;as  dissolved  in  50  cc. 
of  water.  5 cc.  of  concentrated  sulphuric  acid  and  5 g.  of 
calcium  diphenylamine  monosulphonate  added,  then  a solution 
containing  10  g.  of  potassium  chlorate.  The  solution  first 
became  blue  and  then  very  quickly  changed  to  a black.  The 
oxidation  could  not  be  controlled. 


(S4) 


Experiment  VIII. 

Carried  out  the  same  as  experiment  iVII.  hut  potassium 
dichromate  wss  used  in  place  of  the  potassium  chlorate. 

Results  v/ere  the  same  as  in  proceeding  experiment.  Lower- 
ing the  amount  of  acid  and  oxidizing  agent  did  not  change  the 
results* 

ExperimentZIX. 

10  g*  of  the  condensation  product  was  dissolved  in  60  cc. 
of  water  and  5 g.  of  calcium  diphenylamine  mono  sulphonate  added, 
then  5 cc.  of  hydrochloric  acid.  The  solution  was  cooled  and 
15  g.  of  powdered  lead  peroxide  slowly  added  with  agitation. 
Solution  first  turned  light  green  then  became  darker  and  darker 
till  a deep  blue  color  was  reached.  Ammonium  carbonated  was 
added  the  soluble  salt  of  the  dye  filtered  from  the  lead  sludge. 
Resulting  dye  was  a very  green  shade  blue  and  dyed  silk  and  wool 
a very  good  shade. 

Experiment  XX. 

Run  the  same  as  experiment  XIX.  except  that  EO  cc.  of  glacial 
acetric  acid  was  used  in  place  of  the  hydrochloric.  The  solution 
turned  brown  and  then  a very  dark  brown,  as  a final  product. 
Smaller  amounts  of  acetic  acid  gave  practically  the  same  results. 

Experiment  XI. 

Run  the  same  as  experiment  XIX.  except  5 cc.  of  concentrated 
sulphuric  acid  was  used  in  place  of  the  hydrochloric  acid.  The 
reaction  proceeded  much  slower  than  when  hydrochloric  acid  v;as 
used.  Ro  blue  color  developed  for  five  bourse.  Reaction  was 


I 


V. 

i 


j 

< 


s 


[• 


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t 


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I] 


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. t.'  . • 

,.'v  ^ 

. . ..  •.. 

- T -'TTr'  •^rr—  < ".‘‘■:j-?iff*">-'‘j"^" 


J.  •■  J.'.  ./  .J "..  .li ' j 'i  J .'1!!?* 


..  L. 


itFr" 

allowed  to  proceed  36  hours  hy  which  time  it  was  assumed  complete 
The  shade  was  a little  greener  than  v;hen  hydrochloric  acid  was 
used. 

Ammonium  carbonate  was  added  and  the  resulting  dye  filtered 
and  evaporated  to  dryness. 


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V. 

Summary. 

Two  mols  of  diphenyl  amine  to  one  of  sulphuric  acid  v.as 
found  to  he  the  best  ratio  for  the  production  of  diphenylamine 
monosulphonic  acid.  TempeKture  should  he  170  to  180  degrees. 

Condensation  of  calcium  diphenylamine  monosulphorate  with 
formaldehyde  tahes  place  best  in  a neutral  solution  and  with  an 
excess  of  the  latter. 

The  most  satisfactory  oxidizing  agent  was  found  to  he  lead 
peroxide  with  hydrochloric  acid. 


ft 


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Eeferences : 


(27) 


Diphenylaraine  monosulphonic  acid 

V.'inthers  Volume  I Page  571  Patent  Eo.  12,745 

Berichte  " 6.  " 1615 


Diphenyldiaminodiphenylme thane 

V/inthers  Volume  II  " 48  " " 58,072 


Water  Blue 

Winthers  "II  " 149  " " 75,092 

Preparation  para  Puchsine 

Priedlander  Volume  III  " 112 

(1890-94) 


Biaminodiphenyl  Methane 

Priedlander  Volume  III.  " 55 


Anhydro  f ormaldehydeanilin 

Berichte  Volume  XVIII  " 5509 


